EP3573076A1 - Matériau isolant solide, en particulier en forme de bande, formulation pour un agent d'imprégnation permettant de fabriquer un système d'isolation dans un procédé d'imprégnation sous vide et machines dotées d'un tel système d'isolation - Google Patents

Matériau isolant solide, en particulier en forme de bande, formulation pour un agent d'imprégnation permettant de fabriquer un système d'isolation dans un procédé d'imprégnation sous vide et machines dotées d'un tel système d'isolation Download PDF

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Publication number
EP3573076A1
EP3573076A1 EP19000320.2A EP19000320A EP3573076A1 EP 3573076 A1 EP3573076 A1 EP 3573076A1 EP 19000320 A EP19000320 A EP 19000320A EP 3573076 A1 EP3573076 A1 EP 3573076A1
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EP
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Prior art keywords
insulating material
solid insulating
curing catalyst
material according
formulation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
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EP19000320.2A
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German (de)
English (en)
Inventor
Jürgen Huber
Dieter Schirm
Matthias ÜBLER
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Innomotics GmbH
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Siemens AG
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Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP3573076A1 publication Critical patent/EP3573076A1/fr
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/04—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances mica
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
    • B32B19/04—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to another layer of the same or of a different material
    • B32B19/045—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K3/00—Details of windings
    • H02K3/30—Windings characterised by the insulating material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B32B2264/1026—Mica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/04—Insulators

Definitions

  • the invention relates to a solid, in particular band-shaped, insulating material, formulation for producing an insulation system in a Vakuumim Weggnierbacter so and machines with such insulation system, especially for the medium and high voltage range, namely for medium and high voltage machines, especially rotating electrical machines in the medium and high voltage range as well as semi-finished products for electrical switchgear.
  • a circularly propagating magnetic field is generated by time selective energizing, which is the rotor suspended in the bore of the stator and freely rotating, which e.g. due to a large number of applied permanent magnets reacts to the induced magnetic field in the form of forced rotation, drives and thus converts electrical energy into kinetic energy.
  • the laminated core is electrically grounded, while the coils are at a high kilovolt potential.
  • the coils fitted in the stator slots must therefore be electrically insulated against ground potential.
  • each coil with a special mica-based band (so-called mica tape) multiple and defined-overlapped isolated.
  • Mica is used because, as a particulate, in particular as a platelet-shaped, inorganic barrier material, it can effectively retard electrical erosion during partial electrical discharges, for example over the entire service life of the machine or of the generator, and has good chemical and thermal resistance.
  • mica tapes consist of mica paper and one or more carriers, such as fabric, foil (s), which are connected to each other via a tape adhesive. Mica tapes are necessary since mica paper alone does not have the mechanical strength necessary for an insulation process.
  • accelerator substances which initiate the thermal curing of an externally applied impregnating agent: after the coils insulated with mica tape have been fitted into the stator lamination packages and are electrically connected, to prevent partial discharges during later operation eliminates the air in the cavities of the windings and in particular in the groove gaps of the stator core. Since this distance is kept as small as possible from current-fed, insulated coil to the laminated core as a rule, field strengths of several kV / mm are not uncommon. Accordingly, the insulation material is claimed.
  • Thermally curable epoxy resin / anhydride mixtures for vacuum impregnation processes have proven to be suitable as insulation material because they are used for flooding the stators of the electrical machines assembled with their individual parts with the fitted and mica tape-insulated coils.
  • VPI vacuum pressure impregnation
  • the curing catalyst in the mica tape, in the jargon and accelerator, respectively called belt accelerator the curing catalyst in the mica tape, in the jargon and accelerator, respectively called belt accelerator, the task, the applied impregnating agent of epoxy resin and To gel and cure phthalic anhydride in a desired time at a defined temperature.
  • Phtalklareanhydridgemisch As impregnating an epoxy resin Phtalklareanhydridgemisch is used so far.
  • transition metal salts of organic acids and / or substituted amines such as zinc naphthenic salts used in acid anhydride-containing impregnating resins.
  • the glass transition temperatures of the substituted amine derivatives are higher than those of the transition metal salts.
  • the working principle of the generators is inverse to that of the motors.
  • mechanical energy fuel combustion in power plants with turbine drive, by hydropower, etc.
  • the rotor located in the bore is driven, in turn induced in the stator coils electrical currents, which in turn are fed to the network after synchronization.
  • the laminated core is electrically grounded, while the coils are at a high kilovolt potential.
  • phthalic anhydride-free or even anhydride-free, epoxy-based impregnants will be used in the future which are polymerized using curing catalysts.
  • the subject matter of the present invention is a solid insulating material which can be used together with a formulation of an impregnating agent for producing an insulation system in a vacuum impregnation process
  • the insulating material comprises a support, a platelet-like mica barrier material, a first ionic curing catalyst and a tape adhesive
  • the solid insulating material is suitable to be impregnated by a formulation for an impregnating agent in a VPI process for the preparation of an insulation system, wherein the impregnating agent is correspondingly low viscosity, having a viscosity of less than 1500 mPas, preferably less than 500 mPas, more preferably less than 150 mPas at impregnation temperature, characterized in that the impregnating resin is a cycloaliphatic epoxy resin which reacts with the first curing catalyst deposited in the solid insulating material and / or the second curing catalyst dispersed in the formulation of the impregnating agent, the first curing catalyst (“belt accelerator") derived from the solid insulating material being very strong reacts reactively to the cycloaliphatic epoxy groups of the cycloaliphatic epoxy resin in the formulation of the impregnating agent, but sufficiently inert to the functional groups of the tape adhesive also contained in the solid insulating material, so that the storage stability of the solid
  • a cycloaliphatic epoxy resin according to the present invention has at least one oxirane functionality in at least one cycloaliphatic.
  • the epoxy resin for forming a net-like structure in the curing preferably comprises at least two cycloaliphatic rings, wherein - again preferably, both carry at least one oxirane functionality.
  • the subject matter of the present invention is a solid insulating material which can be used together with the formulation of the impregnating agent for producing an insulation system in a vacuum impregnation process, comprising a support, a barrier material, a first curing catalyst and a tape adhesive, wherein the tape adhesive is inert to the first curing catalyst, which under the conditions of vacuum impregnation with the cycloaliphatic epoxy groups of a cycloaliphatic epoxy resin, as contained in the formulation of the impregnating agent, with gelation times of 1 to 15h, preferably 2 to 12, more preferably 2.5 to 10h at impregnation temperature.
  • the use of the insulation system thus produced in electrical machines preferably rotating electrical machines, particularly preferably rotating electrical machines in the medium and high voltage range and in electrical switchgear, medium and high voltage applications, bushings, transformer bushings, generator bushings and / or HVDC bushings, and in corresponding semi-finished article of the invention.
  • the carrier in the solid insulating material is a carrier in the form of woven, e.g. Nonwoven fabric, e.g. Nonwoven, in particular a polyester nonwoven, paper and / or film before.
  • the carrier may also be perforated in the form of a film.
  • this carrier is in the solid insulating material, preferably particulate, barrier material.
  • the barrier material is preferably at least partially platelet-shaped.
  • mica can be used as a barrier material.
  • the tape adhesive connects the at least one carrier and the barrier material in the solid insulating material, the insulation system. It is contained in the solid insulating material in an amount in the range of 1 to 30% by weight, preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight.
  • the first curing catalyst in the solid insulating material in a concentration of 0.001 wt% to 7.5% by weight, for example in the range of 0.001 to 5 wt%, in particular of 0.001 wt% to 2 wt%, and preferably from 0.001 wt% to 1 wt%, before, so that gelation times of several hours can be realized.
  • a second curing catalyst having a light-off temperature of, for example,> 100 ° C, preferably> 120 ° C, more preferably> 140 ° C in the formulation.
  • This second curing catalyst is preferably in a content of 0% by weight - 10% by weight, in particular from 0.01 to 7.5% by weight and particularly preferably in a content of 0.1 to 5% by weight, based on the cycloaliphatic epoxy resin, in the formulation for the impregnating agent ,
  • the first and second curing catalysts are ionically-active curing catalysts.
  • the two cure catalysts can be simultaneously but each of the cure catalysts can also be present alone.
  • an isolation system can be prepared by using only the first and alone using the second curing catalyst
  • an isolation system will be using the first curing catalyst, and most preferably, the isolation system will be prepared using both curing catalysts.
  • the selection of the respective oxirane-containing components, in the solid insulating material of the tape adhesive on the one hand and in the formulation of the impregnating resin on the other hand, is taken so that different Oxiranspezies be selected.
  • a 1,2-terminal oxirane tape adhesive is combined with a cycloaliphatic oxirane as the impregnating resin in the vacuum impregnation process.
  • a tape adhesive based on 1,2-oxirane epoxy resin groups material such as a chain-extended epoxy resin with n ⁇ 1 and / or higher functional epoxy-phenol novolacs are used.
  • a superacid particularly a thermally-activatable superacid, which initiates cationic thermal-driven gelling and cycloaliphatic oxirane epoxy resin during the vacuum impregnation process is suitable.
  • the first curing catalyst initiates the polymerization of the impregnating resin, the cycloaliphatic epoxy resin at temperatures in the range of 20 ° C to 100 ° C, preferably from 50 ° C to 80 ° C and particularly preferably from 55 ° C to 75 ° C.
  • the lowest light-off temperature of the second curing catalyst may also be directly followed by the highest light-off temperature of the first curing catalyst.
  • a filler and / or additives are present in the formulation of the impregnating agent.
  • a filler is present in the form of nanoparticles. It may be particularly advantageous if the nanoparticles are dispersed.
  • the nanoparticles are in the form of polymeric nanoparticles.
  • the nanoparticles are present in the formulation with a particle diameter of 5 nm to 300 nm, in particular with a particle diameter of less than 150 nm.
  • the nanoparticles are present in the formulation in a content of 0.1 to 35% by weight.
  • distilled bisphenol A diglycidyl ether usually has a dynamic viscosity of about 4500 mPa ⁇ s at room temperature, a reduction to the necessary 25-50 mPa ⁇ s by temperature increase manufacturing technology is not feasible.
  • the conversion to distilled bisphenol F-diglycidyl ether with a dynamic room viscosity of about 1500 mPa ⁇ s and ionic polymerization is therefore expedient, as already mentioned in the following German national patent applications, the disclosure content of which is hereby incorporated in the present description: DE 102014219844.5 ; DE 102014221715.6 ; DE 102015205328.8 ; DE 102015202053.3 ; DE 102015204885.3 ,
  • an ionic polymerization is anhydride-free, distilled 1,2-oxirane epoxy resins, for example of the types bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether, expediently.
  • a particularly low viscosity, ie low viscosity, impregnating agent is necessary, which also gels very slowly to ensure complete penetration.
  • the first curing catalyst in the mica tape is therefore advantageously present in a particularly low concentration in order to induce gelling times of several hours.
  • first curing catalysts are preferred in which the glass transition temperature of the cured impregnating agent in the isolation system is greater than 110 ° C., preferably greater than 130 ° C., particularly preferably greater than 150 ° C.
  • first curing catalyst meaning the present in the solid insulating material curing catalyst, a thermally-activatable superacid and / or a thermally-activated super acid derivative, (blocked super acid) such as a complex of a tetrafluoroborate, Sulfoniumderivats, hexafluoroantimonate and / or a hexafluorophosphate as a representative of the so-called superacids or superacid salts.
  • a thermally-activatable superacid and / or a thermally-activated super acid derivative, (blocked super acid) such as a complex of a tetrafluoroborate, Sulfoniumderivats, hexafluoroantimonate and / or a hexafluorophosphate as a representative of the so-called superacids or superacid salts.
  • cure catalysts 5 to 7 have given good results, as in FIG. 2 , Table 1 can be seen
  • thermally activatable superacid derivatives for example, with a crown ether, such as crown ether 15-crown-5, and the like, complexed.
  • a crown ether such as crown ether 15-crown-5, and the like
  • An exemplary complex is AgSbF 6 .
  • such a first curing catalyst initiates cationic, thermally-driven gelation and polymerization of the impregnating resin in the range of 20 ° C to 100 ° C.
  • the impregnating resin is a cycloaliphatic epoxy resin selected from the following compounds: 7-Oxabicyclo [4.1.0] hept-3-ylmethyl-7-oxabicyclo [4.1.0] heptane-3-carboxylate; 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; Bis (3,4-epoxy-cyclohexylmethyl) adipate; Bis (3,4-epoxycyclohexyl) adipate; 4- (1,2-epoxyethyl) -1,2-epoxycyclohexane and / or 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, as well as any mixtures and mixtures of the above-listed compounds.
  • Typical contents for gelling cycloaliphatic epoxy resin with the said first curing catalysts contained in the solid insulating material are much less than 1% by weight, based on the cycloaliphatic epoxy resin of the formulation for the impregnating agent, which first occurs during the vacuum process Hardening catalyst comes into contact.
  • the cycloaliphatic epoxy resin used is 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate , a very low-viscosity epoxy resin which can also be used without reaction diluents and has proven to be very stable on storage.
  • FIG. 1 is a graph showing the temperature-dependent, dynamic viscosity of the cycloaliphatic epoxy resin 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate shows.
  • the first curing catalyst is relatively inert to the tape adhesive material.
  • This especially under the conditions of Vakuumvorhalte- and / or Impregnation temperature for example, in the range between 25 ° C and 100 ° C, in particular between 50 ° C to 80 ° C, most preferably between 55 ° C to 75 ° C.
  • Tape adhesive materials whose main component has only 1,2-oxirane epoxide groups are suitable, for example.
  • Table 1 can be seen, in which the reactivity of the tape adhesive is summarized to different first curing catalysts. Compounds have been identified which have a relatively short gelling time in cycloaliphatic (impregnating resin), but a relatively high storage stability in 1,2-oxirane group epoxy (tape adhesive).
  • the thermally-activated superacids used as curing catalyst 5 to 7 are able to gel extremely rapidly cycloaliphatic epoxy resin at 70 ° C, but are extremely inert compared to conventional 1,2-oxirane containing epoxy resins, which are used as tape adhesive materials in the mica tape.
  • a blocked superacid with a concentration of 0.02% in 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate gives a gelation time of ⁇ 10 h at 70 ° C., with a concentration of 2.5% in one distilled bisphenol-F-diglycidyl ether does not lead to gelation even after 5000 h at 70 ° C.
  • FIG. 3 shows the gelling times (12g, 70 ° C) of these curing catalysts in a cycloaliphatic oxirane. It can be seen that the reactivity of these types of catalysts, although very low in the tape adhesive, the 1,2-oxirane epoxy resin, but very high in the cycloaliphatic epoxy resin, the impregnating resin, so that very low levels of curing catalyst are sufficient.
  • bath curing catalyst additional curing catalyst in the impregnating agent
  • the impregnation resin parts not sufficiently catalyzed by the belt curing catalyst are e.g. experienced in completed folds of the applied mica tape curing during the subsequent annealing process.
  • the potential bath accelerator should of course be soluble in the cycloaliphatic epoxy resin.
  • FIG. 4 shows a list of the compounds used as second curing catalysts, that is to say as so-called bath-curing catalysts, because they are present in the liquid insulating agent.
  • the insulation system according to the present invention may comprise any additives which influence, for example, the coloring, the breaking strength, the fracture toughness, brittleness etc. of the insulation system in the fully cured state.
  • the cured, cycloaliphatic epoxy resin is a very brittle material to which added additives to increase the resistance to fracture and / or to increase the elongation at break become.
  • the addition of flexibilizing auxiliaries such as long-chain polyols, for example polypropylene glycol, may be advantageous.
  • nanoparticles in particular polymeric nanoparticles, as additives.
  • the nanoparticles very effectively increase the elongation at break and fracture mechanical properties of almost comparable glass transition regions.
  • nanoparticle-in-cycloaliphatic EP masterbatches e.g. Polybutadiene core-shell particles, 90-110 nm, agglomerate-free, these particles are e.g. detectable by TEM.
  • These masterbatches contain 25-33% by weight of polymeric nanoparticles and can be used neat or in admixture with the epoxy resin, as in FIG. 5 shown.
  • the first curing catalysts mentioned are (almost) chemically inert with respect to the conventional glycidyl ether-based epoxy resins, for example also epoxy-phenol novolaks which are used as tape adhesives and thus act as highly effective, storage-stable first curing catalysts in the solid insulating material.
  • cycloaliphatic epoxy resins of the type 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate which according to one embodiment of the invention serve as impregnating or impregnating resin, have low dynamic viscosities and allow the impregnation of numerous mica tape layers, in particular in generator construction. Furthermore, they form very high glass transition temperatures during the polymerization initiated by the curing catalyst.
  • An insulation system made with the components described above in the vacuum impregnation process can be used with keep the previously used isolation system of bisphenol A diglycidyl ether EPR162 and methylhexahydrophthalic anhydride EPH868 with respect to the glass transition of greater than 150 ° C (10h / 145 ° C).
  • the inventive combination of a highly effective, inert first curing catalyst in the solid insulating material with the highly flowable cycloaliphatic epoxy resin succeeds in setting high glass transition temperatures without the use of acid anhydrides.
  • This first curing catalyst or a second curing catalyst which is inert in the cycloaliphatic epoxy resin will cure the acid anhydride-free insulating system to give comparable Tgs.
  • This second curing catalyst in the impregnating agent in combination with the first curing catalyst, ensures reliable, complete curing of the entire impregnating agent.
  • This second curing catalyst leads to curing at low levels, more preferably in the range 0.1-5 wt .-%, based on the pure cycloaliphatic epoxy resin.
  • a partial admixture of polymeric nanoparticles in the cycloaliphatic Epoxidharzim Weggnierharz preferably in the form of nanoparticle masterbatches with identical epoxy resin matrix, be useful.
  • a stretching with flexibilizers known to the person skilled in the art based on long-chain diols, such as polypropylene glycols or the like.
  • the invention relates to an insulation system, in particular a winding tape insulation impregnated by means of vacuum impregnation, preferably VPI process, in particular for use in medium and high-voltage machines, in particular rotating electrical machines in the medium and high voltage range.
  • vacuum impregnation preferably VPI process
  • medium and high voltage bushings such as transformer, generator and / or HVDC bushings, as well as in corresponding semi-finished products for electrical switchgear.
  • To optimize the impregnation of the solid insulating material is a cycloaliphatic epoxy resin used as a basis for the formulation of the impregnating agent, while adjustments in the solid insulating material, eg in the mica tape, in relation to the curing catalyst and the tape adhesive are required.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Insulating Bodies (AREA)
  • Insulation, Fastening Of Motor, Generator Windings (AREA)
  • Manufacture Of Motors, Generators (AREA)
  • Organic Insulating Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP19000320.2A 2015-07-17 2016-05-19 Matériau isolant solide, en particulier en forme de bande, formulation pour un agent d'imprégnation permettant de fabriquer un système d'isolation dans un procédé d'imprégnation sous vide et machines dotées d'un tel système d'isolation Pending EP3573076A1 (fr)

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DE102015213537.3A DE102015213537A1 (de) 2015-07-17 2015-07-17 Fester, insbesondere bandförmiger, Isolationswerkstoff, Formulierung für ein Imprägniermittel zur Herstellung eines Isolationssystems in einem Vakuumimprägnierverfahren damit und Maschinen mit derartigem Isolationssystem
PCT/EP2016/061293 WO2017012735A1 (fr) 2015-07-17 2016-05-19 Matériau isolant solide, en particulier sous forme de ruban, formulation pour un produit d'imprégnation servant à la réalisation d'un système d'isolation selon un procédé d'imprégnation sous vide et machines dotées d'un tel système d'isolation
EP16724877.2A EP3304564A1 (fr) 2015-07-17 2016-05-19 Matériau isolant solide, en particulier sous forme de ruban, formulation pour un produit d'imprégnation servant à la réalisation d'un système d'isolation selon un procédé d'imprégnation sous vide et machines dotées d'un tel système d'isolation

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EP19000320.2A Pending EP3573076A1 (fr) 2015-07-17 2016-05-19 Matériau isolant solide, en particulier en forme de bande, formulation pour un agent d'imprégnation permettant de fabriquer un système d'isolation dans un procédé d'imprégnation sous vide et machines dotées d'un tel système d'isolation

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DE102017201498A1 (de) * 2017-01-31 2018-08-02 Siemens Aktiengesellschaft Wickelbandisoliersystem für elektrische Maschinen, Verwendung dazu sowie elektrische Maschine
DE102017125177A1 (de) * 2017-10-26 2019-05-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Elektrisches Bauteil mit Isolationsschicht und Verfahren zu dessen Herstellung
DE102017223876A1 (de) * 2017-12-29 2019-07-04 Siemens Aktiengesellschaft Wicklungsisolation, elektrische Maschine und Fahrzeug
DE102019204190A1 (de) * 2019-03-27 2020-10-01 Siemens Aktiengesellschaft Gießharz, Formkörper daraus und Verwendung des Formkörpers
DE102019207771A1 (de) * 2019-05-28 2020-12-03 Siemens Aktiengesellschaft Additiv, Verwendung dazu, Isolationssystem und elektrische Maschine
DE102019209346A1 (de) * 2019-06-27 2020-12-31 Siemens Aktiengesellschaft Imprägnierformulierung, Isolationsmaterial, Verfahren zum Herstellen eines Isolationsmaterials und elektrische Maschine mit einem Isolationsmaterial
WO2021009842A1 (fr) * 2019-07-16 2021-01-21 三菱電機株式会社 Composition de vernis isolant, bobine de machine rotative et machine rotative
WO2021043541A1 (fr) 2019-09-04 2021-03-11 Siemens Aktiengesellschaft Accélérateur en bande et son utilisation, matériau d'isolation solide et système d'isolation exempt d'anhydride
JP7308799B2 (ja) * 2020-08-31 2023-07-14 東芝三菱電機産業システム株式会社 レジン製造方法及び絶縁構造製造方法
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US20180204649A1 (en) 2018-07-19
RU2018105689A3 (fr) 2019-08-20
AT16858U1 (de) 2020-11-15
CN108028092A (zh) 2018-05-11
RU2018105689A (ru) 2019-08-20
RU2704804C2 (ru) 2019-10-31
US11848123B2 (en) 2023-12-19
CN108028092B (zh) 2021-03-09
EP3304564A1 (fr) 2018-04-11
WO2017012735A1 (fr) 2017-01-26
DE102015213537A1 (de) 2017-01-19
BR112018000745A2 (pt) 2018-09-04

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